EP0443542B1 - Procédé pour la préparation de polyesters à partir d'acides hydroxycarboxyliques - Google Patents
Procédé pour la préparation de polyesters à partir d'acides hydroxycarboxyliques Download PDFInfo
- Publication number
- EP0443542B1 EP0443542B1 EP91102413A EP91102413A EP0443542B1 EP 0443542 B1 EP0443542 B1 EP 0443542B1 EP 91102413 A EP91102413 A EP 91102413A EP 91102413 A EP91102413 A EP 91102413A EP 0443542 B1 EP0443542 B1 EP 0443542B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oligomers
- process according
- opt
- pref
- hydroxycarboxylic acids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000007513 acids Chemical class 0.000 claims abstract description 9
- 230000010933 acylation Effects 0.000 claims abstract description 8
- 238000005917 acylation reaction Methods 0.000 claims abstract description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims abstract description 5
- MTPBUCCXRGSDCR-UHFFFAOYSA-N 4-piperidin-1-ylpyridine Chemical compound C1CCCCN1C1=CC=NC=C1 MTPBUCCXRGSDCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims abstract 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 abstract description 3
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract 3
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 150000002334 glycols Chemical class 0.000 abstract 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 14
- 238000006068 polycondensation reaction Methods 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- -1 isooctyl Chemical group 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- STWODXDTKGTVCJ-UHFFFAOYSA-N 4-pyrrolidin-1-ylpiperidine Chemical compound C1CCCN1C1CCNCC1 STWODXDTKGTVCJ-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KFDKSWDECHPONU-UHFFFAOYSA-N bis(trichloromethyl) carbonate Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl.ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl KFDKSWDECHPONU-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005924 transacylation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
Definitions
- the present invention relates to a process for producing polyesters based on hydroxycarboxylic acids, in particular ⁇ - or ⁇ -hydroxycarboxylic acids or their oligomers, in accordance with the following reaction scheme wherein R, R 'and R''independently of one another are an alkyl radical and / or hydrogen, preferably a lower alkyl radical with 1-6 C atoms and / or hydrogen and particularly preferably a methyl group and / or hydrogen and x and m as well as n integers - where m> n and x can also be zero - can mean.
- Alkyl generally represents an unbranched or branched hydrocarbon radical having 1 to 12 carbon atoms, which may optionally be substituted by one or more halogen atoms, preferably fluorine, which may be the same or different from one another, with lower alkyl radicals being preferred.
- Lower alkyl generally represents a branched or unbranched hydrocarbon radical having 1 to 4 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl and isooctyl.
- triphosgene bis (trichloromethyl) carbonate
- Pyridine or pyridine derivatives are used as acylation catalysts, pyridine or dialkylaminopyridines, as are known from the literature [G. Höfle, W. Steglich and H. Vorbrüggen, Angew. Chem. 90 (1978) 602] are preferred. Pyridine and 4-dialkylaminopyridines are particularly preferably used. Pyridine and 4-dimethylaminopyridine and 4-pyrrolidinopiperidine [W. Steglich and G. Höfle, Angew. Chem. 81 (1969) 1001] and 4-piperidinopyridine.
- polyesters based on hydroxycarboxylic acids in particular of ⁇ - or ⁇ -hydroxycarboxylic acids - especially of lactic acid and / or glycolic acid:
- polyesters with a low molecular weight are accessible by means of such polycondensation reactions [C.H. Holten, Lactic Acid, Verlag Chemie, Weinheim 1971, p. 225 ff].
- ion exchangers as condensation catalysts is said to enable the production of polymers with a molecular weight of approximately 35,000 [EP 26 599].
- polyesters The second approach to such polyesters is the ring-opening polymerization of the corresponding lactides (dilactones). So far, only polymers or copolymers with a molecular weight of MW> 35,000 can be produced in this way.
- the object of the present invention is therefore to provide a process for the preparation of polyesters based on hydroxycarboxylic acids, in particular ⁇ - or ⁇ -hydroxycarboxylic acids, which allows the production of such polyesters with a high molecular weight.
- linking reagents such as CDI, triphosgene or dicyclohexylcarbodiimide - in esterification reactions is known per se from the prior art [J. Ff March, Advanced Organic Chemistry, 3rd Ed., John Wiley and Sons, New York 1985, pp 348th and zit.
- the polycondensation reaction itself can be carried out in the melt or in an inert solvent which does not adversely affect the course of the reaction.
- Suitable solvents are, for example, those solvents which are usually used in polycondensation reactions, which include, inter alia, halogenated hydrocarbons - such as dichloromethane or trichloromethane - or ethers - such as tetrahydrofuran.
- the desired molar mass can be controlled by varying the reaction conditions - temperature, reaction time, molar ratio of monomer or oligomer to transacylation catalyst and in particular of auxiliary or linking reagent to monomer or oligomer.
- linking reagent is necessary.
- an excess of linking reagent - compared to the use of correspondingly purer starting materials - may be necessary.
- phosgene or triphosgene are used as linking reagents
- the purification of the polycondensation product (in particular the separation of low molecular weight reaction products or reacted reactants and also linking reagent) is carried out using the purification processes known from the prior art.
- Hydroxycarboxylic acids - in particular ⁇ - or ⁇ -hydroxycarboxylic acids of the same or different constitution - such as e.g. L-lactic acid, D-lactic acid. Mixtures of D- and L-lactic acid and glycolic acid - or their oligomers and co-oligomers - used.
- the degree of condensation (degree of polymerization) can be varied within a wide range and lie between 1 and approximately 1000. A degree of condensation between 10 and 100 is preferred.
- block polymers such as e.g. Di- or triblock polymers or multiblock polymers.
- Multiblock polymers of L-lactide and D, L-lactide and / or D-lactide may be mentioned as examples.
- the length of the corresponding block in the resulting copolymer can thus be influenced by the appropriate choice of the degree of polymerization of the starting materials. This measure can be used to influence the characteristics of the polycondensation product. End group modification, ie by blocking the terminal hydroxyl or the terminal carboxyl group of the prepolymers, also opens up the possibility of producing diblock polycondensation products.
- the process according to the invention differs in that polycondensation products with higher molecular weights can be produced, which makes polymers accessible which can otherwise only be produced by ring-opening polymerization.
- the process according to the invention has the advantage that it enables a much simpler and therefore more economical method for removing the linking reagent.
- the reaction product is therefore completely free of metal compounds.
- the process according to the invention is a priori superior to those based on the polymerization of lactides, since the oligomers (from which the lactides required to carry out the polymerization first have to be prepared) can be used directly as starting materials in the process according to the invention.
- the method according to the invention enables the production of "random" polycondensates in which there is actually a statistical distribution of, for example, the lactic acid and glycolic acid units, while the polymerization of, for example, glycolide and lactide, due to the higher reactivity of the glycolide, leads to the risk that in the polymer - undesirably - glycolide blocks can occur.
- the viscosity given in the examples was determined in 0.1% solution in chloroform at 25 degrees Celsius.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (13)
- Procédé de préparation de polyesters à base d'acides hydroxycarboxyliques selon le schéma réactionnel suivant
x et m ainsi que n peuvent représenter des nombres entiers, avec m > n et
x peut aussi être nul,
caractérisé en ce que la réaction de condensation est conduite en présence de phosgène, de diphosgène ou de triphosgène. - Procédé selon la revendication 1, caractérisé en ce que la réaction se déroule en présence d'un catalyseur d'acylation.
- Procédé selon la revendication 2, caractérisé en ce que l'on utilise une 4-dialkylaminopyridine comme catalyseur d'acylation.
- Procédé selon la revendication 3, caractérisé en ce que l'on utilise la 4-diméthylaminopyridine comme catalyseur d'acylation.
- Procédé selon la revendication 3, caractérisé en ce que l'on utilise la 4-pipéridinopyridine comme catalyseur d'acylation.
- Procédé selon la revendication 3, caractérisé en ce que l'on utilise la 4-pyrrolidinopyridine comme catalyseur d'acylation.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise des acides α-hydroxycarboxyliques et/ou leurs oligomères.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise des acides β-hydroxycarboxyliques et/ou leurs oligomères.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise des acides α- et β- hydroxycarboxyliques et/ou leurs oligomères.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise l'acide glycolique et/ou ses oligomères.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise l'acide lactique sous forme d'acide D- et/ou L-lactique et/ou ses oligomères.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise l'acide glycolique et l'acide lactique sous forme d'acide D- et/ou L-lactique et/ou leurs oligomères.
- Utilisation du phosgène, du diphosgène ou du triphosgène comme réactifs de liaison lors de la préparation de polyesters à base d'acides hydroxycarboxyliques.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96106159A EP0729992A3 (fr) | 1990-02-21 | 1991-02-20 | Procédé pour la préparation de polyesters à partir d'acides hydroxycarboxyliques |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4005415A DE4005415C2 (de) | 1990-02-21 | 1990-02-21 | Verfahren zum Herstellen von Polyestern auf der Basis von Hydroxycarbonsäuren |
| DE4005415 | 1990-02-21 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96106159.5 Division-Into | 1996-04-19 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0443542A2 EP0443542A2 (fr) | 1991-08-28 |
| EP0443542A3 EP0443542A3 (en) | 1992-10-07 |
| EP0443542B1 true EP0443542B1 (fr) | 1997-06-04 |
Family
ID=6400637
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96106159A Withdrawn EP0729992A3 (fr) | 1990-02-21 | 1991-02-20 | Procédé pour la préparation de polyesters à partir d'acides hydroxycarboxyliques |
| EP91102413A Expired - Lifetime EP0443542B1 (fr) | 1990-02-21 | 1991-02-20 | Procédé pour la préparation de polyesters à partir d'acides hydroxycarboxyliques |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96106159A Withdrawn EP0729992A3 (fr) | 1990-02-21 | 1991-02-20 | Procédé pour la préparation de polyesters à partir d'acides hydroxycarboxyliques |
Country Status (7)
| Country | Link |
|---|---|
| EP (2) | EP0729992A3 (fr) |
| JP (1) | JP3035716B2 (fr) |
| AT (1) | ATE154047T1 (fr) |
| DE (2) | DE4005415C2 (fr) |
| DK (1) | DK0443542T3 (fr) |
| ES (1) | ES2104620T3 (fr) |
| GR (1) | GR3024284T3 (fr) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5444143A (en) * | 1992-12-25 | 1995-08-22 | Mitsui Toatsu Chemicals, Inc. | Preparation process of polyhydroxycarboxylic acid |
| US5543202A (en) * | 1994-03-14 | 1996-08-06 | Kimberly-Clark Corporation | Process for producing a crimp-bonded fibrous cellulosic laminate |
| US5770683A (en) * | 1994-11-02 | 1998-06-23 | Mitsui Toatsu Chemicals, Inc. | Preparation process of polyhydroxycarboxylic acid |
| JPH0959218A (ja) * | 1995-08-25 | 1997-03-04 | Shimadzu Corp | Ｌ−乳酸オリゴマー誘導体 |
| US5719256A (en) * | 1995-10-19 | 1998-02-17 | Mitsu Toatsu Chemicals, Inc. | Process for preparing polycondensation polymer compound |
| EP0817619A4 (fr) * | 1996-01-24 | 1999-02-03 | Us Army | Nouvelles microspheres de poly-(lactide/glucolide) a liberation prolongee "sans eclatement" |
| CA2485512C (fr) | 2002-05-08 | 2011-03-22 | Japan Science And Technology Corporation | Nouveau polyester comprenant un groupe a conjugaison-.pi. dans la chaine laterale et un materiau de transport de charge utilisant celui-ci |
| EP1382628A1 (fr) * | 2002-07-16 | 2004-01-21 | Polyganics B.V. | Segment- ou block-copolyester phase-separée |
| JP2004359582A (ja) * | 2003-06-03 | 2004-12-24 | Tendou Seiyaku Kk | 環状乳酸オリゴマー２倍量体の製造方法 |
| JP4621885B2 (ja) * | 2004-05-07 | 2011-01-26 | 独立行政法人物質・材料研究機構 | ポリリンゴ酸共重合体の製造方法 |
| JP2008291268A (ja) * | 2008-07-07 | 2008-12-04 | Toray Ind Inc | ポリ乳酸ブロック共重合体の製造方法 |
| KR101027163B1 (ko) | 2009-12-18 | 2011-04-05 | 주식회사 엘지화학 | 폴리락타이드 수지, 이의 제조 방법 및 이를 포함하는 폴리락타이드 수지 조성물 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE344034C (fr) * | ||||
| US4622413A (en) * | 1984-08-31 | 1986-11-11 | Ppg Industries, Inc. | Method for preparing amino acid ester hydrohalides |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1495626B1 (de) * | 1960-03-30 | 1971-06-09 | Bayer Ag | Verfahren zum herstellen von polyestern |
| US4273920A (en) * | 1979-09-12 | 1981-06-16 | Eli Lilly And Company | Polymerization process and product |
| US4438253A (en) * | 1982-11-12 | 1984-03-20 | American Cyanamid Company | Poly(glycolic acid)/poly(alkylene glycol) block copolymers and method of manufacturing the same |
| JPS60229919A (ja) * | 1984-04-27 | 1985-11-15 | Mitsubishi Chem Ind Ltd | ポリエステル、ポリエステルアミドおよびポリアミドの製造法 |
| CA1256638A (fr) * | 1984-07-06 | 1989-06-27 | Motoaki Tanaka | Polymere, et sa production |
| JPH01167329A (ja) * | 1987-12-23 | 1989-07-03 | Idemitsu Kosan Co Ltd | ポリエステル、ポリエステルアミドまたはポリアミドの製造法 |
| US4877871A (en) * | 1988-06-14 | 1989-10-31 | Nabisco Brands, Inc. | Synthesis of sucrose polyester |
-
1990
- 1990-02-21 DE DE4005415A patent/DE4005415C2/de not_active Expired - Fee Related
-
1991
- 1991-02-20 JP JP3049080A patent/JP3035716B2/ja not_active Expired - Fee Related
- 1991-02-20 AT AT91102413T patent/ATE154047T1/de not_active IP Right Cessation
- 1991-02-20 EP EP96106159A patent/EP0729992A3/fr not_active Withdrawn
- 1991-02-20 DK DK91102413.1T patent/DK0443542T3/da active
- 1991-02-20 DE DE59108729T patent/DE59108729D1/de not_active Expired - Fee Related
- 1991-02-20 ES ES91102413T patent/ES2104620T3/es not_active Expired - Lifetime
- 1991-02-20 EP EP91102413A patent/EP0443542B1/fr not_active Expired - Lifetime
-
1997
- 1997-07-30 GR GR970401933T patent/GR3024284T3/el unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE344034C (fr) * | ||||
| US4622413A (en) * | 1984-08-31 | 1986-11-11 | Ppg Industries, Inc. | Method for preparing amino acid ester hydrohalides |
Non-Patent Citations (1)
| Title |
|---|
| J. ORG. CHEM., Band 33, Nr. 11, November 1968, Seiten 4173-4176; H.L. WEHRMEISTER et al.: "Total synthesis of the macrocyclic lactone, dideoxyzearalane" * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04216822A (ja) | 1992-08-06 |
| EP0443542A2 (fr) | 1991-08-28 |
| EP0729992A2 (fr) | 1996-09-04 |
| EP0729992A3 (fr) | 1997-01-15 |
| JP3035716B2 (ja) | 2000-04-24 |
| EP0443542A3 (en) | 1992-10-07 |
| DK0443542T3 (da) | 1997-06-23 |
| GR3024284T3 (en) | 1997-10-31 |
| DE4005415C2 (de) | 1996-04-11 |
| DE59108729D1 (de) | 1997-07-10 |
| ATE154047T1 (de) | 1997-06-15 |
| ES2104620T3 (es) | 1997-10-16 |
| DE4005415A1 (de) | 1991-08-22 |
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